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Ortiz Weiss-Penzias Total and Mmhg in Terrestrial Arthropods from Central Bull Environ Contam Toxicol DOI 10.1007/s00128-014-1448-6 Total and Monomethyl Mercury in Terrestrial Arthropods from the Central California Coast Cruz Ortiz Jr. • Peter S. Weiss-Penzias • Susanne Fork • A. Russell Flegal Received: 17 July 2014 / Accepted: 19 December 2014 Ó Springer Science+Business Media New York 2014 Abstract The aim of this project was to obtain a baseline Keywords Atmospheric Á Mercury Á Terrestrial Á understanding and investigate the concentration of mercury Bioaccumulation Á Invertebrates (Hg) in the tissue of terrestrial arthropods. The 4-month sampling campaign took place around Monterey Bay, Cali- fornia. Total mercury (HgT) concentrations (x ± SD, dry The novelty, scientific significance, and importance weight) for the captured specimens ranged from 22 to of the Article 188 ng g-1 in the Jerusalem crickets (Orthoptera: Stenopel- matidae); 65–233 ng g-1 in the camel crickets (Orthoptera: The novelty and the importance of this study is that it’s Rhaphidophoridae); 25–227 ng g-1 in the pill bugs (Isopoda: creating a baseline understanding of mercury cycling in Armadillidiidae); 19–563 ng g-1 in the ground beetles terrestrial ecosystems. Unfortunately, there are very few (Coleoptera: Carabidae); 140–441 ng g-1 in the variegated other studies of mercury in terrestrial arthropod food chains meadowhawk dragonflies (Odonata: Libellulidae); for comparison. Hopefully this initial report will catalyze 607–657 ng g-1 in the pacific spiketail dragonflies (Odonata: new studies on the role of atmospheric deposition in the Cordulegastridae); and 81–1,249 ng g-1 in the wolf spiders biogeochemical cycling of mercury in terrestrial ecosys- (Araneae: Lycosidae). A subset of samples analyzed for tems. Moreover, the role of arthropods on the bioaccu- monomethyl mercury (MMHg) suggest detrital pill bugs have mulation and biomagnification of mercury in terrestrial a higher MMHg/HgT ratio than predatory ground beetles. food chains. Lastly, this investigation falls within BECT’s aims and scope because it characterizes variations of mercury contamination. The motivation for this study came from an investigation which received significant press- C. Ortiz Jr. Á P. S. Weiss-Penzias Á A. R. Flegal coverage in 2012–2013 \http://green.blogs.nytimes.com/ Institute of Marine Science, University of California - Santa 2012/03/28/coastal-california-fog-carries-toxic-mercury- Cruz, 1156 High Street, Santa Cruz, CA 95064, USA study-finds/[. e-mail: [email protected] Historic and on-going mercury contamination is of A. R. Flegal increasing concern for environmental and human health, as e-mail: fl[email protected] its toxic threshold continues to be lowered (Agency 2013; C. Ortiz Jr. (&) Organization 2010). That concern is based on the extensive Department of Environmental Engineering Sciences, bioaccumulation (factor of 107) of organic mercury to Engineering School of Sustainable Infrastructure and potentially toxic levels, especially in aquatic food chains Environment, University of Florida, 412 Black Hall, PO Box 116450, Gainesville, FL 32611-6450, USA (Fitzgerald et al. 2007; Scheulhammer et al. 2007). As a e-mail: cortiz@ufl.edu result, most research on the biomagnification of mercury has focused on aquatic environments. Arthropods are an S. Fork important source of protein for many organisms (Zhang Elkhorn Slough National Estuarine Research Reserve, PO Box 267, Moss Landing, CA 95039, USA et al. 2009); furthermore, a few recent studies have deter- e-mail: [email protected] mined that terrestrial food chains may be contaminated by 123 Bull Environ Contam Toxicol the cross-habitat transfer of mercury by insects and spiders arthropods: ground beetles (Coleoptera: Carabidae) (Brasso and Cristol 2008; Cristol et al. 2008; Henderson (n = 14), wolf spiders (Araneae: Lycosidae) (n = 58); et al. 2012). pacific spiketail dragonflies (Odonata: Cordulegastridae) Limited published data exist on Hg concentrations in (n = 2); and variegated meadowhawk dragonflies (Odo- terrestrial arthropods, and their potential as Hg pollution nata: Libellulidae) (n = 4). The adult dragonflies were bioindicators needs further investigation. Terrestrial captured with sweep nets, all the other arthropods were arthropods whose tissue is resistant to metallic pollutants captured using pit fall traps; these methods of collection are are often used as biological indicators for metal contami- described elsewhere (Chanthy et al. 2013; Greenslade nation in soil (Dallinger et al. 1992; Udovic et al. 2009). It 1964). Unbaited pitfall traps were deployed 2–4 consecu- is also recognized that flying arthropods such as mosqui- tive nights and checked within 24 h of deployment. toes may also be a useful indicator of atmospheric Hg The samples were placed in trace metal clean plastic contamination (Hammerschmidt and Fitzgerald 2005). containers, within a cooler, and then promptly transported Thus, the current study aimed to evaluate the efficacy of to UCSC. There they were rinsed with high purity using arthropods as indicators of Hg accumulation by (18.2 MX cm) water (Milli-QÒ) to remove surface con- measuring the concentration of Hg in the tissue of terres- taminants. Then they were dried, placed in trace metal trial arthropods from the central California coast, an clean plastic containers, frozen, and lyophilized prior to environment well known for its persistent summer-time fog analysis. (Weiss-Penzias et al. 2012). Mercury analyses were made using established trace metal clean techniques. The organisms (29–249 mg) were weighed (±0.1 mg), pulverized, transferred to 100 mL Methods and Materials acid-cleaned volumetric flasks, and digested with 10–20 mL of H2SO4–HNO3, using the methodology Samples were collected, using trace metal clean techniques described elsewhere (Liang et al. 1994). HgT concentra- at 3 sites around Monterey Bay, California: (1) Elkhorn tions in digestates were then determined by cold vapor Slough Estuarine Reserve (2) the University of California, atomic fluorescence spectrometry (CVAFS) with estab- Santa Cruz (UCSC), and (3) Chalk Mountain in An˜o Nu- lished methods that quantitatively measure Hg in aqueous evo State Park (Fig. 1). The 4-month arthropod sampling samples (Bloom and Fitzgerald 1988; Fitzgerald and Gill campaign took place between March and October of 2012. 1979). MMHg concentrations of six samples were then The samples included detrital arthropods: Jerusalem measured by CVAFS after distillation, aqueous ethylation, crickets (Orthoptera: Stenopelmatidae) (n = 7), camel purge and trap (Liang et al. 1994). The accuracy of the HgT crickets (Orthoptera: Rhaphidophoridae) (n = 11), and pill measurements was determined from concurrent analyses of bugs (Isopoda: Armadillidiidae) (n = 41); and predatory (1) procedural blanks, (2) Hg0 calibration standards, (3) Fig. 1 Map of study location, Monterey Bay, California with sample sites at Elkhorn Slough Reserve (36°49012.700N, 121°44010.700W), the University of California, Santa Cruz (36°59028.500N, 122°03040.700W), and Chalk Mountain in An˜o Nuevo State Park (37°09037.900N, 122°17024.800W) 123 Bull Environ Contam Toxicol National Research Council of Canada Certified Reference arthropods delineated in this study. There was notable tem- Material (CRM) DORM-2 (dogfish muscle), (4) replicate poral differences, although not statistically different aliquots from sample digests, and (5) replicate subsamples (p B 0.05), in HgT concentrations of some of the arthropods of arthropod digests from the parent samples. Three or in our study (Table 2). Although these comparisons might be more standard solutions were made for each analysis. All an artifact of a small sample size, they warrant further inves- analyses had standard regressions with simple linear cor- tigation. Total mercury concentrations in wolf spider had relation coefficients (R2) greater than 0.998. The HgT relatively comparable HgT concentrations in March procedural blank ranged between 11 and 25 parts per tril- (255 ± 97 ng g-1,n= 28), July (278 ± 127 ng g-1, lion (ppt), and the HgT concentration of the CRM (DORM- n = 5, and October (327 ± 173 ng g-1,n= 20), but those 2) ranged between 98 and 102 % of its certified value average concentrations were all less than half of the average (4.64 ± 0.26 lgg-1). HgT concentration of wolf spiders in August (846 ± 312 ng g-1,n= 5). The temporal difference coin- cided with the seasonal peak of fog that substantially increases Results and Discussion the flux of MMHg in the study site. A similar, albeit much smaller, seasonal increase was also observed in camel crick- There is a lack of published values in the literature for ets, but not pill bugs (Fig. 2). Fog data reported for 2012 was comparison; furthermore, the values published have a very obtained from Monterey Regional Airport (MRY); mean daily high variance, as is the case with this study. HgT con- visibility below 15.5 km is the threshold for reported fog centrations (x ± SD, dry weight) of the 134 insects and occurrences at MRY and is indicative of a foggy day. spiders measured in this study, along with HgT values The positive covariance of high HgT concentrations in previously reported for some of those organisms (Cristol wolf spiders, and to a much lesser extent in camel crickets, et al. 2008; Rimmer et al. 2010; Zhang et al. 2009) are does not seem to correspond with any known variables. listed in Table 1. There is no statistically difference Since the life span of male wolf spiders is about a year, (p B 0.05, t test) in HgT concentrations among any of the with most adolescents in February through March (Punzo species measured at the different sites, those comparisons and Farmer 2006), HgT concentrations in the spiders are limited by the high variance of mercury values. For should have been highest in October if that uptake was example, the relative standard deviation (%) of HgT in simply due to temporal bioaccumulation. And since the spiders in our study was 73.6 ng g-1 (n = 58) and that in camel cricket population is relatively constant over time, the study by Cristol et al.
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